Separation of organic compounds



Jan 29, 1952 J. M. wRlGl-n'soN SEPARATION OF' ORGANIC COMPOUNDS Filed June 28, 194'? ATTORN EYS .a portion Vof the treating Patented Jan. 29, 1952 `2,583,620 SEPARA'AIION OFORGANIC COMPOUNDS John M. Wrightson, `North-Bergen,TN, J., assigner vto The W.

Kellogg Company, Jersey City,

N .J .,a corporation AofDelaware 4 Application .June-28, 1947, SerialNo.-757,'912 i I6 Claims.

This invention relates to the separation of organic compounds and relatesmore `particularly to the separation of organic compounds from lthe reaction product obtained in the reduction fof oxides of carbon with hydrogen inthe presence of a catalyst at elevated temperatures. Still more particularly, the invention'relates to an improved process for the separation and recovery of oxygenated organic compounds and hydrocarbons obtained from the condensation of reactor gases produced in the catalytic hydrogenation of oxides of carbon.

In the hydrogenationlof oxidesof carbon in the presence of a catalyst at elevated tempera tures, a reaction product is obtained in the form of reactor outlet gases at temperatures varying between about-300 F. to about 700 F; and co`n taining hydrocarbons and oxygenated organic compounds comprising organic acids, alcohols, aldehydes, ketones, and esters. Thesegasesare passed through one or more Vcondensationrones in which they are cooled to temperatures Within the range from about 40 F. toiabout 1509i'. tto effect separation of a condensate, `this condensate ultimately separating into "an aqueous phase and an oil or hydrocarbon-rich phase. Both vphases comprise oxygenated organic compounds, fthose of lower molecular weight 4tending to remain lin the aqueous phase while those of Vhigher molecular Weight tend to remain inthe oil productor non-aqueous liquid phase.

I have found that the aforementioned oil product, or a fractionated portion thereof, comprising a mixture of hydrocarbons and oxygenated organic compounds, consisting of organic acids, alcohols, aldehydes, ketones and esters, may be subjected to extraction with a glycol `solvent treating agent to extract the aforementioned oxygenated organic compounds from theoil, 'the particular glycol solvent treating agent selected having a boiling point higher than that of the oxygenated compounds subjected to extraction. In addition, I have found that in `carrying out this extraction, optimum results are obtained in employing a glycol treating agent `whose boiling point is below that of the lowest boiling ihydro-' carbon present in the aforementioned mixture, although the choice of a suitable glycolsolvent treating agent is not necessarily restricted to femploying a glycol solvent having `the aforementioned characteristics. When the boiling npoint of the treating agent is approximatelylequal :gto or above the boiling point of the lowestlboiling hydrocarbon component ,present lin the mixture, agentY employed in the Aalcohol azeotropes fand hydrocarbons.

:alcohol-hydrocarbon `extraalction `step `may distill over and necessitate further separation of hydrocarbonsfrom the solvent treating agent in the rainate thus .pro-

-ing agent, also contains relatively smaller quantities of hydrocarbons. VUpon separation of the `solvent treating agent, AI `have found that the Vremaining mixture of `oxygenated organic compounds and hydrocarbons `canbe contacted with 5a `light alcohol treating agent and upon subse- -quent distillation of the mixture thus produced,

relatively pure oxygenated` organic compounds may be separated from fthe remaining hydrocarbons, the latter being taken `overhead as their These azeotropes may be next resolved into their alcohol and hydrocarbon ,components by successive extraction and distillation as more fully shown in the process herein- :after described.

The present invention, is, therefore, particularly directed to a process as more fully hereinafter described for the separation and recovery of hydrocarbons `and oxygenated organic compoundspresent inthe oil `product obtained from the `condensation of reactor vgases produced in the aforementioned catalytic` hydrogenation of oxides of carbon. In general, 4the invention broadly comprisesrst subjecting the aforementioned oil product, or a fractionated Yportion ithereof, to a rst extraction treatment with a glycol solvent vfor oxygenated organic vcompounds present in the oil, to obtain an extract compris- Jing oxygenated organic compounds. and a minorv `portion ofthe hydrocarbons present. The extract thus obtained is transferred` to arstdis- `tillation step to separate the solventcontained therein from oxygenated organic `compounds The `separated solvent .next recycled to the `iirst extraction step, andthe .mixture of loxygenated organic compounds and :hydrocarbons obtained :from the aforementioned distillation step `is `contacted witha light alcohol treating agenttoiform a minimum boiling azeo- `trope with 'the hydrocarbons I,contained in this mixture. The resulting mixture of alcohol-hydrocarbon azeotropes and oxygenated organic 4`compounds is transferred to a second distillation -Step to separate the oxygenated compounds rfrom the azeotropes thus produced. The separated azeotropes are Vnext sub- 4extraction vtreatment Awith extract comprising lthe 4alco- Ijected to -a second water to4 obtain an 2,583,620 .Y 3 4 hol treating agent and water and a raiilnate organic compounds comprising organic acids, alcomprisins the Separated hydrocarbons. The concis, a1dehydes,ketones, and esters, and is first eXtlaC thus Produced iS transferred 130 a third cooled to condense substantially large quantities distillation step in which the alcohol treating of normally liquid components. Convenientagent is separated from the water and is recycled 5 ly, condensation may be effected in a plurality of to the second distillation step, while water thus @001mg Stages which are represented diagramseparated is recycled to the second extraction matically in the drawing by cooler i3 with which step. l z line I2 connects. From cooler I3, the resulting The 'rainate obtained from the above-menmixture of condensate and uncondensed gases tioned first extraction step comprises a mixture passes through line I4 to a separator i5. In the of hydrocarbons and small quantities of absorbed 1 latter, uncondensed gases are withdrawn through glycol solvent treating agent.V This mixture is line I6 and recycled through this line to the synnext subjected to a third extraction treatment thesis feedin line I0, with which line I5 connects. with water to obtain an extract comprising the The-condensate in separator I5 separates as a solvent treating agent and water-and a rai-"Linate '1ower aqueous phase and an upper oil phase. comprising the separated hydrocarbons." The "'The'aque'ous phase is drawn off from the botextract thus produced is subjected todistillation j Etorn of separator I5 through line I'I for further to separate the solvent treating agent from water., use or treatment outside the scope of the present Water thus separated is recycled to Ithe' aboveprocess, and the oil phase is drawn off at an inmentioned extraction step while the separated termediate point through line I8. It should be soltenttreatingagent is recycled to the first exnoted that apparatus embodying more than one Vtraction step. y separation stage may be employed if desired; for i .It is, therefore, an object of this inventionv to example, primary and secondary stages may be provide an improved process for the separation of introduced, operating successively and respechydrocarbons organic acids, alcohols, aldehydes, tively at temperatures of about 150 F. and about `ketones, and esters from mixtures thereof. F.

Another object of the invention is to provide an improved process for the separation of hydro- `rcarbons and oxygenated organic compounds present in the oil product obtained `from the con- 'densation of reactor gases produced in the catavlytic hydrogenation of oxides of carbon.

v Other objects and advantages inherent in the -present invention will be apparent in the following more detaileddisclosure. The accompanying drawing illustrates, diagrammatically, one form of the apparatus employed and capable of carrying out one embodiment of the process of my invention. While the 'v invention will be described in detail by'reference' to one embodimentof the process employing the apparatus illustrated in the drawing, it should be noted that it is not intended that theinven- The oil product liquid phase withdrawn from separator I5 through line I8 comprises a mixture of hydrocarbons and oxygenated organic compounds consisting of organic acids, alcoholsaldehydes, ketones, and esters. This oil product or a fractionated portion thereof, boiling within the range from about F. to about 400 F. is next subjected to further treatment in the process hereinafter described. Where it is desired to treat a fractionated portion of the aforementioned oil product in line I8, the total oil product may be transferred through line I8 to any suitable separation zone or series of separation zones,

illustrated in the drawing by separation unit I9, from which an oil fraction boiling within the aforementioned temperature range may be separated in the manner known to those skilled in the art. This oil fraction is withdrawn from separation unit I9 through line 2li and comprises ,-a mixture of hydrocarbons and the aforementioned oxygenated organic compounds. Thismixture is next subjected to extraction treatment vwith a glycol solvent treating agent to Vextract oxygenated organic compounds from the oil, the particular glycol selected having a boiling point higher than that of the oxygenated compounds subjected to extraction. Accordingly, I prefer to tion be limited to the embodiment as illustrated, [but is capable of other embodiments which may' c extend beyond .the scope of the apparatus illus- .LtratedV Pumps, compressors, valves, and other `mechanical elements necessary to effect the 'Li transfer of liquids and vapors and to maintain the'conditions of temperature and pressure nec- 1 essary to carryout the function of the kapparatus, are omitted in order to simplify the description. It will be understood, however, that much y equipment' of this nature is necessary and will .use ethylene glycol, which boils at a temperature I be supplied bythose skilled in the art. Y 1.varying between about 388.4" F. and about 392 Referring to the drawing, the aforementioned 55 F. and has been found overall generally satis- I synthesis feed comprising a reaction mixture of factory as a solvent treating agent in effecting -1 .hydrogen and an oxide of carbon, at varying mol extraction of substantially all of the oxygenatratios.. such as 2:1, respectively, is supplied ed compounds present in the aforementioned through line I0 and transferred through thisvv mixture. In addition to employing ethylene gly- ;line to a synthesis reaction vessel, representedin col as a solvent treating agent in the aforementhe drawing by reactor II. In reactor II, the tioned extraction step, I may use other glycol solk.reaction mixture is contacted with a hydrogena- 4 vents, which are higher boiling than ethylene tionV catalyst, such as a reduced iron or .cobalt Aglycol thus efecting total extraction of all oxycatalyst, at temperaturesvarying between about l 3007 F. and about 700 F., and at pressures .Varyr ing between about atmospheric pressure and about 500 pounds per square inch, and is car- Y ried out according to conventional fixed bed or tioned mixture. ,noted that in carrying out the aforementioned extraction, it is desirable to employ a glycol treating agent having a boiling point lower than that genated compounds present in the aforemen- In this respect, it should be uid bed operations. The resulting reaction product obtained from reactor II is withdrawn through line I2. This product is in the vapor form, substantially as it comes from the reactor treating agent is equal to or higher boiling than within `the aforementioned temperature range, the boiling point of the lowest boiling hydrocontaining water, hydrocarbons and 'oxygenatedl 75`-carbon component present'in the mixture, a poro--of the lowest boiling hydrocarbon present in the hydrocarbon-oxygenated organic compounds mixture. Where the boiling point of the glycol tion of thefsolvent in varying quantities, may

distill over and necessitate further separation of hydrocarbonsfrom the solvent treating agent in the raffinate thus produced, as provided for and more fully hereinafter described, in the process of the invention. Hence, in additionlto ethylene glycol as an overall Vgenerally `suitable solvent treating agent, other glycols may besuccessfully employed such as l\,-3butanediol; 1,6-hexanediol; diethylene glycol, isopropylene glycol, triethylene glycol Land trimethyleneglycol. 0f theseglihave found LS-butanediol, which `boils at approximately 399.2D F. and 1,6-hexanediol, which boils at approximately 482 F., `generally preferable as glycol solvents which are higher ,boiling than ethylene glycol, although it should be understood that other glycols which meet the aforementioned requirement may be successfully employed as solvent treating `agents in accordance with the process of the invention.

The aforementioned mixture of hydrocarbons and oxygenated organic compounds comprising organic acids, alcohols, aldehydes, ketones, and esters, is transferred through line 2c to a low point in an extraction tower 2|. In tower 2 i, the mixture introduced through line 20 is subjected to intimate countercurrent contact with a selected glycol solvent treating agent, such as ethylene glycol, which is introduced into tower 2i at an upper point through line 22. The treating agent and the aforementioned mixture are contacted in tower 2| under conditions effective to absorb in the treating agent substantially all of the oxygenated organic compounds present. The extract thus produced is withdrawn yfrom the bottom of tower 2| through line 23. The separated hydrocarbons in tower 2| may be withdrawn overhead through line 24 for further use or treatment outside the scope of the present process. In instances where the boiling point of the glycol treating agent is equal to or higher than the boiling point of the lowest boiling hydrocarbon present in the aforementioned mixture, a portion of the solvent may distill over in the raflinate withdrawn through line 24. This mixture may ybe next transferred from line 24 through line 25, Awith which line 24 connects, for further separation of hydrocarbons from the glycol solvent in the process hereinafter described.

The extract from the bottom of tower 2!! comprises a mixture of the glycol solvent treating agent, the aforementioned oxygenated organic compounds andproportionately small quantities of hydrocarbons. This mixture is next transferred through line 23 to a distillation tower 2,6. In tower Z the mixture is heated under condi'- tions of temperature and pressure eiective to distill overhead the lower boiling material which comprises a mixture of oxygenated organic compounds and proportionately small quantities of hydrocarbons, which are withdrawn through line 2'! for further treatment in the process l1erein after described. The higher boiling fraction from tower 2t, comprising the separated glycol treating agent, is withdrawn through line 28 and transferred into line 22, with which line 28 connects, for further use in tower 2| as previously described. Make-up solvent is `supplied through line 2S, with which line 22 connects.

As described above the overhead from tower 2t comprising a mixture of oxygenated organic compounds and proportionately small quant-ities ofhydrocarbons is withdrawn through line 2l. This mixtureis 1next contacted with alight alrcohol, such ,as .methanoh ethanol or propanoL `Ito form minimum boiling ifa'zeotropes with hydro carbons contained in the mixture. In this re spect, it should -be noted "that `any alcohol `may be added tothe aforementionedmixture, whose boiling point is below that of thelowest rboiling oxygenated organic compound `or hydrocarbon present, and which can form a minimum boiling azeotrope `withthese hydrocarbons. Any hydrocarbons which do not form an azeotrope withthe added alcohol treating agent (forexample, pentane which does not forma Aminimum .boiling azeotrope with propanol) would be takenoverheadztogether with the hydrocarbon-alcohol.aseotropes upon'subeequentdistillation. Accordingly, a suitable light alcohol treating agent, such as methanol which is Yillustrated in the drawing, `is added to the mixture 'of hydrocarbons and oxygenated organic compounds inline 2'?, through line 3c. The mixture oi `oxygenated organic compounds and alcoholLhydrocarbon azeotropes thus produced, is next transferred through line 2'! toa-distillation tower 3|. Tower 3| is heated under proper operating conditions of temperature and pressure eifective fto-idistil1 overhead the aforementionedmethanol-hydrocarbon azeotropes which are withdrawn through line 32. Bottoms from tower 3| comprising a mixture or" oxygenat-ed Iorganic compounds consisting of or ganic acids, alcohols, aldehydes, ketones, and esters are withdrawn through line 33 and may be subjected to further 1treatment for the separation of individual components inthe manner known to those skilled in the `art.`

As described above, methanol-hydrocarbon azeotropes are distilled overhead :from tower 3| and withdrawn through line 32. These azeotropes are next transferred through .line 32 to a low point in an extraction tower 34. In `order to effect 4separation of Lmethanol and hydrocarbon components present in the aforementioned azeotropes, these azeotropes introduced into tower 3ft through line 32 are subjected to intimate coun# tercurrent contact with water, Vregulated to in troduce suiiicient quantities to `remove methanol or the particular alcohol treating agent present, `from hydrocarbons comprising the aforementioned azeotropic mixture in tower 3B. Water thusemployed is introduced into tower 3d at an upper point through :line 35. Following `countercurrent `contact .in tower 34 between the methanol-hydrocarbon azeotropes and the introduced water, separation .is effected between an `upper hydrocarbon `phase and a .lower aqueous phase comprisingchiey water containingsmall amounts of methanol. The upper phase in tower 34 thus obtained, comprising substantially pure hydrocarbons is withdrawn .through lino te and may be subjected to further treatment 'for the separation of individual 4hydrocarbon compo- Lnents in the manner known to those skilled in theart.

The lower aqueous phase from Vtower 3d, containing small amounts fof methanol, comprises the extract obtained from subjecting 'the methanol-hydrocarbon azeotropes, introduced into tower 34 through linei35, to countercurrent extraction with water. Thisrextract 'is withdrawn from the bottom oi' tower 34 through line3l and is transferred to a distillation tower 3B. In tower 38 the aqueous methanol extract obtained from tower 34 is heated under proper operating conditions of temperature and pressure eiective to dehydrate methanol or the particular selected alcohol I.treating agent. As Varesult of distilla- Ation Sin, .tower 38 an overhead .is :obtained comprising methanol which is withdrawn through line 3D and recycled through this line to line 21, with which line 30 connects, for further use as the alcohol treating agent in tower 3| in the process hereinbefore described. Make-up methanol is ksupplied through line 39, with which line 30 connects. Bottoms from tower 38 comprising water are transferred through line 35, for further use in tower 34 in the process hereinbefore described. Make-up quantities of water are supplied through line 40 with which line 35 connects.

As previously described, the mixture of hydrocarbons separated in tower 2| and withdrawn in the overhead ramnate through line 24 may also contain a portion of the glycol solvent treating agent, in instances where the boiling point oi the glycol treating agent is equal to or higher than the boiling pointl of the lowest' boiling hydrocarbon present. VThis mixture may be next transferred from line 34 through line 25, with which line 24 connects, to a low point in an extraction tower 4|. In tower 4| the mixture introduced through line is subjected to intimate countercurrent contact with water as a treating agent, which is introduced into tower 4| in an upper point through line 42. The hydrocarbon-glycol mixture and water are contacted in tower 4I under conditions effective to absorb in the water, substantially all of the glycol solvent present in the mixture passing through line 25. As a result of the extraction process in tower 4I, an upper hydrocarbon or oil layer and a lower aqueous glycol layer are produced. The upper hydrocarbon layer from tower 4| is withdrawn as an overhead raii'inate through line 43 and may be subjected to further treatment for the separation of individual hydrocarbon components in the manner known to those skilled in the art and outside the scope'of the present process. The extract from tower 4|, comprising an aqueous glycol layer is withdrawn as bottoms through line 44 and transferred to a distillation tower 45. Tower 45 is operated under proper conditions of temperature and pressure effective to distll water overhead which is withdrawn through line 42 and transferred through this line for further use in the extraction process in tower 4| as described above. Make-up water is introduced into line 42 through line 46 with which line 42 connects. Bottoms from tower 45 comprising the glycol solvent treating agent, substantially water-free, are withdrawn through line 22 and recycled through this line for further use as the solvent in tower 2| in the process hereinbefore described.

To recapitulate, this invention is directed to an improved process for the separation and recovery of oxygenated organic compounds and hydrocarbons obtained from the condensation' of reactor gases produced in the catalytichydrogenation of oxides oi carbon. However, while the invention has been described as having a particular applicability to the separation of such compounds obtained from the source indicated, it should be noted that the process of the invention is not necessarily restricted to effect the desired separation of these compounds as derived from the aforementioned source. The process of the invention may be also successfully applied to the separation of any mixtures of the aforementioned compounds with regard to the source from which these mixtures may .have been .derived and without regard to the composition of such mixturesi Inithis respect, it should be S noted that it is possible to introduce such mixtures directly into tower 2|, through line 20 for treatment in the process hereinbefore described.

In addition, while a particular embodiment o1" this invention has been described for purposes of illustration, it should 'be understood that various modifications and adaptations thereof, which will be obvious to one skilled in the art, may be made within the spirit of the invention as set forth in the appended claims.

Having thus described my invention, what I claim and desire to secure by Letters Patent is:

l. In a process for the hydrogenation oi oxides of carbon in which is recovered a hydrocarbonrich phase comprising a mixture of hydrocarbons and oxygenated organic compounds as a product of said hydrogenation and boiling within the range between about 15)D F. and about 400' F., the method of treating at least a portion of said hydrocarbon-rich phasewhich comprises subjecting said portion to a first extraction treatment with a glycol solvent for said oxygenated organic compounds wherein said solvent is higher boiling than the oxygenated organic compounds subjected to extraction, to obtain an extract comprising oxygenated organic compounds and a minor portion of said hydrocarbons and a i'ai'linate comprising a major portion oi said hydrocarbons, separately subjecting said extract to a rst distillation to separate it into a relatively high-boiling fraction containing solvent and a relatively low-boiling fraction containing oxygenated organic compounds and hydrocarbons, contacting said relatively lowboiling fraction with a light alcohol treating agent to form a minimum boiling azeotrope with hydrocarbons contained in said fraction, subjecting the resulting mixture to a second distillation to separate oxygenated organic compounds from said alcohol-hydrocarbon azeotrope, subjecting said azeotrope to a Second extraction treatment with water to obtain an extract comprising said alcohol treating agent and water and a raiiinate comprising hydrocarbons, and subjecting said last-mentioned extract to a third distillation to separate it into a relatively low-boiling fraction containing said alcohol treating agent and a relatively high-boiling iraction containing water. f

2. A method as defined by claim l said glycol solvent is ethylene glycol.

3. A method as defined by claim l said glycol solvent is 1,3-butanediol.

4. A method as defined by claim l said glycol solvent is 1,6-hexanediol.

5. A method as deiined by claim l wherein said light alcohol treating agent is methanol.

5. A method as defined Aby claim l wherein said light alcohol treating agent is ethanol.

7. A method as dened by claim l wherein said light alcohol treating agent is propanol.

8. In a process for the hydrogenation of oxides of carbon in which is recovered a hydrocarbonrich phase comprising a mixture of hydrocarbons and oxygenated organic compounds as a product of said hydrogenation and boiling within the range between about F. and about 400 F., the method of treating at least Va portion of said hydrocarbon-rich phase which comprises subjecting said portion to a rst extraction treatment with a glycol solvent for said oxygenated organic compounds wherein said solvent is higher boiling than the oxygenated organic compounds subjected to extraction, to obtain an extract comprising oxygenated organic compounds and a wherein wherein Whelelll `minor portion of said` hydrocarbonsi` and a cohol treating` agent and water anda raiinate comprising hydrocarbons.

9. In a process for the hydrogenation or'oxides of carbon in which is recovered a hydrocarbonrich phase comprising a mixture oi' hydrocarbons and oxygenated organic compounds as a product of said hydrogenation and boiling within the range between about 150 F. and about dell the method of treating at least a portion o1 said hydrocarbon-rich phase which comprises subjecting said portion to a first extraction treatment with a glycol solvent for said oxygenated organic compounds wherein said solvent is higher boiling than the oxygenated organic compounds subjected to extraction, to obtain an extract comprising oxygenated organic compounds and a minor portion of said hydrocarbons and a rainnate comprising a major portion of said hydrocarbons, contacting said extract with a light alcohol treating agent to form a minimum boiling aceotrope with hydrocarbons contained in said extract, separately recovering oxygenated organic compounds and said alcohol-hydrocarbon azeotrope from the resulting mixture, and subjecting said azeotrope to a second extraction treatment with water to obtain an extract comprising said alcohol treating agent and water and a raflinate comprising hydrocarbons.

lo. In a process for the hydrogenation of oxides of carbon in which is recovered a hydrocarbonrich phase comprising a mixture of hydrocarbons and oxygenated organic compounds as a product of said hydrogenation and boiling within the range between about 150 F. and about 400 F., the method of treating at least a portion of said hydrocarbon-rich phase which comprises sui,- jecting said portion to a first extraction treatment with a glycol solvent for said oxygenated organic compounds wherein said solvent is higher boiling than the oxygenated organic compounds subjected to extraction, to obtain an extract comprising cxygenated organic compounds and a minor portion of said hydrocarbons and a raiiinate comprising a major portion of said hydrocarbons, contacting said extract with a light alcohol treating agent to form a minimum boiling azeotrope with hydrocarbons contained in said extract, and separately recovering oxygenated organi-c compounds and said alcoholhydrocarbon azeotrope from the resulting mixture.

11. A method for treating a mixture of hydrocarbons and oil-soluble oxygenated organic compounds boiling within the range between about 150 F. and about 400 F. which comprises subjecting said mixture to g rst extraction treatment with a glycol solvent for said oxygenated organic compounds wherein said solvent is higher boiling than the oxygenated organic comraiinate comprisinga' drocarbons,` separately e 10 pounds subjected" to extraction,` to obtain"an=.ex tract comprising oxygenated organic compounds and a minor portion of said hydrocarbons anda major portion of saidA hysubjectingI said extract i to i alrst distillation to separate it into a relatively thigh-boiling fraction containingsolvent and a "relatively low-boiling fraction containing oxywith a'ilight alcohol treating genated` organic compounds and hydrocarbons, contacting said relatively low-boiling fraction agent to form a minimum boiling azeotrope with hydrocarbons contained inlsaid fraction, subjecting-the resulting mixture to a second distillation to separate oxygenated organic compounds from said alcoholhydrocarbon azeotrope, subjecting said azeotrope to a second extraction treatment with vwater to obtain an extract comprising said alcohol treating agent and water and a rallinateV comprising hydrocarbons, and subjecting said last-mentioned extract to a third distillation to separate it into a relatively low-boiling fraction containing said alcohol treating agent and a relatively high boiling fraction containing water.

12. A method for treating a mixture of hydrocarbons and oil-soluble oxygenated organic compounds boiling within the range between about F. and about 400 F. which comprises subjecting said mixture to a first extraction treatment with a glycol solvent for said oxygenated organic compounds wherein said solvent is higher boiling than the oxygenated organic compounds subjected to extraction, to obtain an extract comprising oxygenated organic compounds and a minor portion of said hydrocarbons and a rafnate comprising a major portion of said hydrocarbons, separately subjecting said extract to a rst distillation to separate it into a relatively high-boiling fraction containing solvent and a relatively low-boiling fraction containing oxygenated organic compounds and hydrocarbons, contacting said relatively low-boiling fraction with a light alcohol treating agent to form a minimum boiling azeotrope with hydrocarbons contained in said fraction, subjecting the resulting mixture to a second distillation to separate oxygenated organic compounds from said alcohol-hydrocarbon azeotrope, and subjecting said azeotrope to a second extraction treatment with water to obtain an extract comprising said alcohol treating agent and water and a rainate comprising hydrocarbons.

1.3. A method for treating a mixture of hydrocarbons and oil-soluble oxygenated organic compounds boiling within the range between about 150 l5'. and about 400 F. which comprises subjecting said mixture to a iirst extraction treatment with a glycol solvent for said oxygenated organic compounds wherein said solvent is higher boiling' than the oxygenated organic compounds subjected to extraction, to obtain an extract comprising oxygenated organic compounds and a, minor portion of said hydrocarbons and a raffinate comprising a major portion of said hydrocarbons, contacting said extract with a light alcohol treating agent to form a minimum boiling azeotrope with hydrocarbons contained in said extract, separately recovering oxygenated organic compounds and alcoholhydrocarbon azeotrope from the resulting mixture, and subjecting said azeotrope to a second extraction treatment with water to obtain an extract comprising said alcohol treating agent and water and a rainate comprising hydrocarbons.

14. A method for treating a mixture of hydro- 

1. IN A PROCESS FOR THE HYDROGENATION OF OXIDES OF CARBON IN WHICH IS RECOVERED A HYDROCARBONRICH PHASE COMPRISING A MIXTURE OF HYDROCARBONS AND OXYGENATED ORGANIC COMPOUNDS AS A PRODUCT OF SAID HYDROGENATION AND BOILING WITHIN THE RANGE BETWEEN ABOUT 150* F. AND ABOUT 400* F., THE METHOD OF TREATING AT LEAST A PORTION OF SAID HYDROCARBON-RICH PHASE WHICH COMPRISES SUBJECTING SAID PORTION TO A FIRST EXTRACTION TREATMENT WITH A GLYCOL SOLVENT FOR SAID OXYGENATED ORGANIC COMPOUNDS WHEREIN SAID SOLVENT IS HIGHER BOILING THAN THE OXYGENATED ORGANIC COMPOUNDS SUBJECTED TO EXTRACTION, TO OBTAIN AN EXTRACT COMPRISING OXYGENATED ORGANIC COMPOUNDS AND A MINOR PORTION OF SAID HYDROCARBONS AND A RAFFINATE COMPRISING A MAJOR PORTION OF SAID HYDROCARBON, SEPARATELY SUBJECTING SAID EXTRACT TO A FIRST DISTILLATION TO SEPARATE IT INTO A RELATIVELY HIGH-BOILING FRACTION CONTAINING SOLVENT AND A RELATIVELY LOW-BOILING FRACTION CONTAINING OXYGENATED ORGANIC COMPOUNDS AND HYDROCARBONS, CONTACTING SAID RELATIVELY LOWBOILING FRACTION WITH A LIGHT ALCOHOL TREATING AGENT TO FORM A MINIMUM BOILING AZEOTROPE WITH HYDROCARBONS CONTAINED IN SAID FRACTION, SUBJECTING THE RESULTING MIXTURE TO A SECOND DISTILLATION TO SEPARATE OXYGENATED ORGANIC COMPOUNDS FROM SAID ALCOHOL-HYDROCARBON AZETROPE, SUBJECTING SAID AZEOTROPE TO A SECOND EXTRACTION TREATMENT WITH WATER TO OBTAIN AN EXTRACT COMPRISING SAID ALCOHOL TREATING AGENT AND WATER AND A RAFFINATE COMPRISING HYDROCARBONS, AND SUBJECTING SAID LAST-MENTIONIED EXTRACT TO A THIRD DISTILLATION TO SEPARATE IT INTO A RELATIVELY LOW-BOILING FRACTION CONTAINING SAID ALCOHOL TREATING AGENT AND A RELATIVELY HIGH-BOILING FRACTION CONTAINING WATER. 